Weed oil-fertilizer composition



United States Patent 3,272,613 WEED OIL-FERTILIZER COMPOSITION Donald C.Young, Fullerton, Calif., assignor to Union Oil Company of California,Los Angeles, Calif, a corporation of California No Drawing. Filed Sept.4, 1962, Ser. No. 221,350 7 Claims. (Cl. 712.3)

This invention relates to liquids comprising a hydrocarbon oilemulsified in ammonium salt solutions, to an emulsifiable concentratecomprising said oil, emulsifier and water and to methods forpreparingsaid emulsion and said emulsifiable concentrate.

In recent years, petroleum stocks have been sprayed over weed growth inorchards and citrus groves to check the growth of weeds. This practicechecks weed growth while resulting in better water penetration and lesserosion of soil than encountered with cultivation. A substantialreduction in time and expense of this application could be effected ifthe weed spraying were combined with fertilization of the orchard orcitrus grove by emulsifying the weed oil in a fertilizer solution.Unfortunately, ammonium salt solutionsthe commonly employedfertilizersare liquids which are extremely resistant to emulsification.

It is an object of this invention to provide a stable emulsion of ahydrocarbon oil in ammonium salt solutions.

It is also an object to provide an emulsifiable oil composition whichwill spontaneously emulsify in ammonium salt solutions.

I have found that hydrocarbons can be stably emulsified in ammonium saltsolutions with an emulsifier comprising an amine salt of asulfo-dicarboxylic acid ester of polyoxyethylated alkylphenols. Ingeneral, chemicals having the following structure are suitable as theemulsifier:

R2 S 03X wherein:

-X is an organic amine cation;

n is an integer between about 2 and about 5; and the total of carbons inany R R or R group is less than about 12; and preferably less than about6.

Examples of suitable radicals from which R and R can be selected are thefollowing: methyl, ethyl, propyl, isopropyl, butenyl, isobutyl, amyl,isoamyl, heptenyl, isoheptenyl, octyl, isooctenyl, nonyl, isononyl,decenyl, isodecyl, undecyl, isoundecenyl, dodecyl, isododecyl, etc.

Examples of various R groups are the following: methylene, ethylene,propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene,hexylene, isohexylene, etc.

Various organic amine cations can be used for X such as the primary,secondary and tertiary alkyl, alkenyl and aryl amines as well asheterocyclic compounds containing a basic nitrogen. Examples of suitableamines are the following: methylamine, dimethylamine, ethylamine,triethylamine, diethyl benzyl amine, propyla mine, isopropylamine,diisopropylamine, ethylpropylamine, butyla-mine, isobutyla-mine,diisoamylamine, hexylamine, heptylamine, isooctylamine, furanamine,benzylamine, morpholine, pyridine, etc. Preferred are the alkylarnineshaving between 1 and about 6 carbons, e.g., isopropylamine.

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Examples of various compounds useful as emulsifiers in my invention arethe following: half isobutyl amine salt, half tetraethoxy xylenol esterof sulfo-gluteric acid; half isopropyl amine salt, half triethoxy amylphenol ester of sulfo-adipic acid; half amyl amine salt, halfpentaethoxy cresol ester of sulfo-pimelic acid; half hexylamine salt,half diethoxyoctyl phenol ester of sulfo-suberic acid; halfisopropylamine salt, half diethoxy dodecyl phenol ester of sulfo-azelaicacid; half heptylamine salt, half diethoxy dodecyl phenol ester ofsulfo-sebacic acid, etc.

Of the aforedescribed emulsifier compounds, the most preferred are thosein which the total of carbons in any R R or R group is less than 4 andthe number of carbons in the R group is 2 or 3. In this most preferredgroup, n preferably equals two.

The ammonium salt solutions which are used as the liquid medium in whichthe hydrocarbon oil is emulsified are, in general, the conventionalliquid fertilizer solutions such as aqua ammonia, ammonium nitrate,monoammonium phosphate, diammonium phosphate, ammonium sulfate, ammoniumsulfide, ammonium chloride and mixtures thereof. In general, aqueoussolutions of the aforementioned solutes are used having at least about 5weight percent of solute. Preferably, the emulsion is formed with moreconcentrated solutions, e.g., those having salting out temperatures ator about 0 C. Typically, the following concentrations can be used; aquaammonia, 20-0-0; ammonium nitrate, 20-0-0; ammonium phosphate, 8-24-0;and ammonium sulfate, 10-0-0.

Various hydrocarbon oils can be used as the herbicide such as virgin andconverted crude oil distillates and residues, e.g., stove oils, fueloils, gas oils, diesel oils, aromatic extracts and acid sludges fromrefined distillates, etc. A class of materials readily available andhaving a preferably high concentration of aromatics comprises thevarious petroleum residues from crude distillation and thermal andcatalytic cracking. Aromatic stocks boiling between about 250 and 550 F.are preferred because of their apparent high toxicity. Examples ofaromatic types are benzene, alkylbenze-nes having one, two or threealkyl side chains, each having from 1 to 20 carbons. Naphthalene,'methylnaphthalenes, dimethylnaphthalenes, ethylnaphthalenes,diethylnaphthalenes, decahydronaphthalene, tetrahydronaphtalene,anthracene, alkyl anthracenes, phenanthrene, pyrene, etc.

If desired, the toxicity of the hydrocarbon can be fortified by theaddition of various toxic compounds such as dinitrobutyl phenol,dinit-roa-myl phenol, pentachlorophenol or commonly used broad leafherbicides such as 2-4, dichlorophenoxyacetic acid, salts and alkanolesters thereof to the emulsion in amounts comprising from about 2 toabout 50 weight percent of the total organic content of the emulsion;although amounts from about 2 to 15 percent of the organic content wouldbe most useful.

The amount of hydrocarbon in the fertilizer emulsion can be widelyvaried, as desired, from about 10 to about 50 weight percent of theemulsion. The amount so employed will depend largely on the relativerates of application desired. In general, 20 to pounds of oil per acreperye-ar will provide adequate weed control; however, the first year ofuse as much as 300 pounds per acre may be required, this amount to beapplied in tw-o or more applications.

The degree of fertilization varies with the crops; however, generallyabout 50 and about 200 pounds of nitrogen per acre are required for mostcrops and citrus. Preferably "between about 15 and 200 pounds ofphosphorus (as P 0 and/or sulfur are also applied. The aforementionedblend of hydrocarbon and fertilizer will adequately satisfy theserequirements; preferably, however, emulsions containing between about 30and about 45 weight percent of a hydrocarbon oil are employed.

3 4 The balance of the emulsion comprises the aforemen- COMPOSITION 3tioned aqueous ammonium salt so t and sufiicleut of Residual f el Oil 50the aforementioned emulsifiers to form a stable emulsion. Half amylamine half tetraethoxy Xylene} ester In general, the emulsifier isemployed In amounts 60111- of lf l t i i 10 prising between about 1 and25 weight percenll; of tlge hy 5 L 1 ,Onlium sulfate solution 40drocarbon; preferably in amounts between a out an 20 weight percent.COMPOSITION 4 The aforementioned emulsifiable concentra e c pr r maticlube oil extract 30 between about 5 and about 50 weight percent ofwater, 'bel heptyl amine Salt, h lf diethoxydodecyl tween about 49 andabout 94 weight percent of a. hydrophenol ester f lfo ba i id 6 carbonoil and between about .5 and abo 1 w lg pf go-04 ammonium nitrate 64cent of an emulsifier. Preferably, to avoid excessive di utions, thewater content of the concentrate is maintained at COMPOSITION 5 aminimum value and is between about 5 and about 25 Dimethylnaphthalene(mixture of 2,6 and 2,7) 25 weight percent. Half isopropylamine, halftriethoxy amyl phenol The hydrocarbon oil and emulsifier can be readilyemulether of sulfo-adipic acid 1 sified in the ammonium salt solution bystirring in a mix 9 O-0-10 ammonium sulfate 74 tank the amountspreviously indicated. The order of mixing the components is notmaterial, although it is pre- COMPOSITION 6 ferred to have theemulsifier present when the oil and Aromatic gas oil (SOD-850 F. boilingpoint) 40 ammonium salt solution are mixed. Half diisopropyl amine salt,half diethoxy cresol Simple mixing of water, oil and emulsifier,however, is ether of sulfo-pimelic acid 81 not sufiicient to form theemulsifiable concentrate of my 20 0-0 ammonium nitrate 20 invention. Ihave found that an apparent electrostatic 8-24-0 ammonium phosphate 32charge accumulates on the separate phases during mixing E l 1 and thischarge does not dissipate during normal mixing. xamp e The emulsifiableconcentrate, therefore, must be stirred A commercial weed oil, Union OilCompany of Calunder conditions to dissipate the apparent electrostaticifornia, Solvent 4276, having a boiling point range of charge whichprevents thorough dispersion of the liquids. about 420 to about 760 F.and comprising chiefly a The electrostatic charge can, of course, beremoved by catalytically cracked light cycle oil, was emulsified atapplying a voltage to the liquid mixture, e.g., by immersseveralconcentrations in ammonium nitrate with varied ing electrodes into themix tank. Preferably, however, amounts of an emulsifier. In the firstseries of experiintermittent mixing is performed in an electricallyments, the half amine salt, half polyethoxy alkyl phenol grounded tank.The tank contents are stirred for a periether of a sulfo-dicarboxylicacid was employed as the 0d of 2 to 15 minutes, agitation isdiscontinued for 2 to emulsifier. The following table summarizes theresults:

TABLE 1 Weight Ratio Volume, ml. Separation 1 Emulsifier Sample Wt.percent One Hour 20 Hours 4 Days Oil Ammonium Oil Ammonium of OilNitrate Nitrate O C A O C i 010 A 25 119 81 1.0 68 13 110 79 1 120 so 1120 50 25 119 81 5.0 1 170 31 2 05 104 3 so 113 50 25 119 81 10.0 175 312 98 107 3 so 118 50 25 119 31 20.0 187 27 1 108 105 2 92 120 50 25 11981 25.0 198 18 'I'r 121 05 4 98 114 50 35 104 100 1.0 1 174 31 10 100 90100 4 102 50 35 104 100 5.0 192 17 2 121 so, 2 109 98 50 35 104 100 16 1126 84 2 112 07 50 35 104 100 9 Tr 151 71 2 12s 02 50 35 104 100 5 Tr166 50 4 134 88 1 Separation reported as milliliters of oil layer (0),

2 Tr is trace.

15 minutes, then again applied for 2 to 15 minutes. Repetition of thisagitation for 2 to about 5 cycles will generally cause completeemulsification whereas several hours of continuous agitation will failto achieve emulsification.

The following compositions are illustrative of hydrocarbonoil-fertilizer compositions within the scope of my invention:

COMPOSITION 1 8-240 ammonium phosphate solution 89 COMPOSITION 2Aromatic distillate, 300450 F. boiling range 35 Half ethyl amine salt,half diethoxy (o-cumenol) ester of sulfo-succinic acid 4 20-0-0 ammoniumnitrate solution 61 cream or emulsion layer (0) and aqueous layer (A).

When the experiment is repeated with other types of emulsifiersincluding the following: Dupanol SN, sodium lauryl sulfate; Teigitol 4,7-ethyl 2-methy1 undecano1-4 sodium sulfate; Triton X-100, isooctylphenol polyethoxy ethanol; Egepal 630, nonyl phenoxy polyoxyethyleneoxide; Ultra-Wet 30DS, polyalkyl benzene sulfonate with an average Calkyl group; no stable emulsion is formed.

The preceding examples are intended solely to illustr-ate my inventionand are not to be construed as unduly limiting thereof, the scope of myinvention being intended to be defined by the following claims.

I claim:

1. A concentrate spontaneously emulsifiable in concentrated aqueousammonium salt solutions to provide weed oil-fertilizer compositionscomprising between about 49 and 94 weight percent of a hydrocarbon oil,between about 5 and 50 weight percent water and between about 0.5 and 19weight percent of an emulsifier characterized by the following:

wherein:

R is selected from the class consisting of alkyl and alkenyl groups;

R is selected from the class consisting of hydrogen,

alkyl and alkenyl groups;

R is selected from the group consisting of trivalent sulfo-alkylene andsulfo-alkenylene; X is an organic amine cation having from 1 to about 6carbon atoms;

n is an integer between about 2 and about land the total of carbons ineach of R R R groups is less than about 12.

2. The composition of claim 1 wherein the total of carbons in each ofsaid R R and R groups is less than about 6.

3. The composition of claim 1 wherein the total of carbons in each ofsaid R R and R groups is less than about 4 and n equals two.

4. A weed oil-fertilizer composition comprising an emulsion of betweenabout and about 50 weight percent of a hydrocarbon oil emulsified in anaqueous ammonium salt solution with an emulsifier in an amountcomprising between about 5 and about Weight percent of said hydrocarbon,said emulsifier characterized by the following:

0 o oc..... o t l,. t ox R2 S 03X wherein:

R is selected from the class consisting of alkyl and alkenyl groups; Ris selected from the class consisting of hydrogen,

alkyl and alkenyl groups; R is selected from the group consisting oftrivalent sulfo alkylene and sulfo-a1kenylene; X is an organic aminecation having from 1 to about 6 carbon atoms; n is an integer betweenabout 2 and about 5; and the total of carbons in each of R R R groups isless than about 12. 5. The composition of claim 4 wherein said ammoniumsalt solution is ammonium nitrate.

6. The composition of claim 4 wherein the total of carbons in each ofsaid R R and R groups is less than about 4 and n equals 2.

7. The composition of claim 4 wherein said aqueous ammonium saltsolution is saturated with said ammonium salt at a temperature of about0 C.

References Cited by the Examiner UNITED STATES PATENTS 2,898,267 8/ 1959Lindner 167-42 2,976,209 3/1961 Lindner 167-42 2,976,211 3/1961 Lindner712.3 3,080,280 3/1963 Lindner 712.3

DONALL H. SYLVESTER, Primary Examiner.

ANTHONY SCIAMANNA, H. R. CAINE, Examiners.

1. A CONCENTRATE SPONTANEOUSLY EMULSIFIABLE IN CONCENTRATED AQUEOUSAMMONIUM SALT SOLUTION TO PROVIDE WEED OIL-FERTILIZER COMPOSITIONSCOMPRISING BETWEEN ABOUT 49 AND 94 WEIGHT PERCENT OF A HYDROCARBON OIL,BETWEEN ABOUT 5 AND 50 WEIGHT PERCENT WATER AND BETWEEN ABOUT 0.5 AND 19WEIGHT PERCENT OF AN EMULSIFIER CHARACTERIZED BY THE FOLLOWING: